Sulfonated phenolic material and its use in post primary oil recovery

ABSTRACT

Sulfonated phenolic compounds as well as sulfomethylated phenolic compounds, surfactant systems containing such compound and the use of such surfactant systems in post primary oil recovery are disclosed.

This invention relates to new chemical compounds. In another aspect,this invention relates to a new surfactant system. In still anotheraspect, this invention relates to post primary oil recovery employing anew surfactant system.

BACKGROUND OF THE INVENTION

Water flooding and surfactant flooding are processes well known in theart to recover the vast quantities of oil which remain in the formationafter primary oil recovery operations. Designing new surfactant systemsof high oil recovery efficiency and good phase stability remains a goalin this technology.

THE INVENTION

It is one object of this invention to provide a new chemical compositionuseful in oil recovery.

Another object of this invention is to provide a process for theproduction of such a new chemical composition which is inexpensive andemploys readily available starting materials.

A further object of this invention is the provision of a surfactantsystem useful in surfactant flooding. Particularly the surfactant systemshould be useful in environments comprising hard brines.

Yet another object of this invention is to provide an oil recoveryprocess using the surfactant system of this invention.

These and other objects, advantages, details, features and embodimentsof this invention will become apparent to those skilled in the art fromthe following detailed description of the invention and the appendedclaims.

In accordance with this invention, a new chemical composition orrespectively a mixture of new chemical compositions is provided whichcan be broadly characterized as a sulfonated alkyl substituted phenolicmaterial. It has been found that such compositions, or mixtures of suchcompositions, are useful surfactants in post primary oil recovery.

SULFONATION REACTION

In accordance with a first embodiment of this invention, a process toproduce the sulfonated phenolic material of this invention is provided.This process is characterized by a reaction between one or more alkyl oralkenyl substituted phenolic compounds in either a sulfonation reactionor a sulfomethylation reaction.

In both variations of this process embodiment the starting material forthe sulfonation reaction, or respectively the sulfomethylation reaction,is a phenolic material which can be broadly characterized as an alkylsubstituted hydroxyaryl compound having an unsubstituted aromatic carbonatom in an ortho position with respect to the phenolic hydroxylsubstitution. The starting material used can also be characterized bythe formula ##STR1##

wherein Ar is an aromatic hydrocarbyl moiety having the --OH and the --Xin ortho position to each other, so that --OH and --X are attached toneighboring aromatic carbons, which aromatic hydrocarbyl moiety may befurther substituted by one or more --OH groups and/or hydrocarbylsubstitutents.

wherein --X is hydrogen,

wherein R is an alkyl or alkenyl radical having 1 to 30 carbon atomswith the proviso that at least one radical R has 6 to 30 carbon atoms,

wherein n is 1, 2 or 3,

and wherein the total number of carbon atoms in all n radicals R and inthe aromatic moiety Ar together is 12 to about 40, with the furtherproviso that the total number of phenolic --OH groups in the molecule ispreferably 1 to 3 and most preferably 1 or 2.

This phenolic starting material carrying a sulfonatable orsulfomethylatable aromatic C-H configuration is subjected to one of thefollowing chemical reactions.

Sulfonation

The sulfonation of the alkyl substituted phenolic material can becarried out in a variety of ways which are basically known in the art.Among the sulfonation agents that can be used are fuming sulfuric acid,SO₃, a solution of SO₃ in SO₂, concentrated sulfuric acid and the like.The sulfonation reaction is generally carried out utilizing a slightexcess of the sulfonating agent. The sulfonating conditions includetemperatures in the range of -30° to 150° C. and reaction times in therange of a few minutes to several hours. The pressure for thesulfonation reaction is generally such that the ingredients remain inthe liquid phase under the utilized temperature conditions.

The sulfonated alkyl substituted phenolic material obtained in the abovedescribed reaction can be separated from the reaction mixture. Thesulfonic acid produced in the sulfonation step is generally neutralizedprior to or following the above mentioned separation step. It is,however, also within the scope of this invention to employ thesulfonation mixture after neutralization as such in post primary oilrecovery to be described in the following.

The neutralization of the sulfonic acid formed in the sulfonation of thephenolic starting material is advantageously carried out by contactingthe sulfonated alkyl substituted phenolic compound with a base. Amongthe bases useful for this neutralization step the alkali metal oxidesand hydroxides, and in particular the sodium and potassium oxides andhydroxides, and the ammonium and amine bases are preferred. The ammoniumand amine bases can be broadly characterized by the formula

    NR.sub.3.sup.(1)

with or without water, wherein R.sup.(1) is hydrogen, alkyl having 1 to3 carbon atoms, and hydroxy alkyl with 2 or 3 carbon atoms, preferably 2carbon atoms.

The base employed in the neutralization reaction is usually used in aslight stoichiometric excess. The neutralization step is carried out ata temperature generally in the range of 20° to 100° C. while thepressure is maintained to keep the reacting mass essentially in theliquid phase. The neutralization reaction is generally terminated in afew minutes.

It is within the scope of this invention and under certain circumstancesit is preferred to use the sulfonation reaction product as such withoutprior separation in the neutralization step and to use a neutralizedsolution as such in post primary oil recovery without prior separationstep.

The sulfonation reaction and subsequent neutralization results in asulfonate surfactant which is particularly desirable in surfactantflooding operations for post primary oil recovery. The chemical formulaof the sulfonate salt is ##STR2##

wherein R, Ar are as defined above and wherein Y.sup.(1) is --SO₃ --Catwherein Cat stands for --Na, --K, --NHR₃.sup.(1) with R.sup.(1) havingthe same meaning as above.

Sulfomethylation

In accordance with a second variation of this embodiment of thisinvention, novel chemical compositions are produced by asulfomethylation reaction of the alkyl or alkenyl substituted phenolicstarting materials defined above. This sulfomethylation reactioninvolves the reaction between the phenolic starting material,formaldehyde and a sulfonating agent. The presently preferredsulfonating agents are alkali metal sulfites or bisulfites, ammoniumsulfite or ammonium bisulfite, or amine salts characterized by theformula

    (NR.sub.3.sup.(1) H).sub.1 or 2 H.sub.1 or 0 SO.sub.3

wherein R.sup.(1) has the same meaning as defined above. Theformaldehyde as well as the sulfite compounds are employed in thissulfomethylation reaction approximately in stoichiometric quantities,i.e., one molecule of each compound is used per phenolic hydroxyl groupof the phenolic starting material. The formaldehyde and the sulfite canbe used in slight excess. The sulfomethylation reaction is carried outunder temperature in the range of 0° to 150° C. while the pressure ismaintained high enough to keep the reactants in the liquid state. Thetime for the sulfomethylation reaction will generally be in the range ofa few minutes to 24 hours.

The sulfomethylated product produced in accordance with this inventionis believed to constitute a novel composition of matter.

The Compounds of This Invention

Both the sulfonated and the sulfomethylated phenolic compounds arebelieved to be novel compositions of matter. The preparation of thesecompounds has been described above.

The novel compositions of this invention can be generally characterizedby the following formula ##STR3##

wherein R, Ar and n have the meaning as defined above and Z is selectedfrom the group of radicals consisting of --SO₃ --Cat and --CH₂ --SO₃--Cat, with Cat having the same meaning as described and defined above.The radical Z and the --OH group are both attached to the aromatic ringstructure Ar and are in ortho position relative to each other. The totalnumber of carbon atoms in all n radicals R and the aromatic moiety Artogether is in the range of 12 to about 40.

The total number of phenolic --OH groups in the molecule will be 1 to 3preferably 1 or 2; the molecule will usually not contain more than threesulfonate substituents, and preferably will have 1 or 2 of suchsulfonate substituents. Particularly preferred are compounds which havejust one sulfonate substituent.

In the following, some examples of phenolic structures are given. Inthese examples, the structures refer to both the starting materialphenols as used in the process for producing the novel sulfonated ormethyl sulfonated compounds as well as the final products. X, Y and Zhave the meanings as defined above and X, being hydrogen, refers to thestarting phenolic material while the substituents Y and, respectively, Zrefer to the sulfonated or respectively methyl sulfonated products.Examples of the phenolic molecule structure are given in the following:##STR4## mono- or dialkyl phenols and their sulfonated orsulfomethylated counterparts; ##STR5## alkylated bisphenols and theirsulfonated and sulfomethylated counterparts; R.sup.(2) is H or CH₃##STR6## mono- and dialkyl 4-hydroxy naphthols and their sulfonated andsulfomethylated counterparts.

Surfactant System

A further embodiment of this invention is a surfactant system. Thissystem comprises brine, a sulfonated or sulfomethylated phenoliccomposition as defined above and a cosurfactant.

The surfactant system of this invention optionally contains a protectiveagent. Water is used containing a certain quantity of sodium chloridefor practical reasons. Typical and preferred compositions of asurfactant system of this invention are shown in the following table.

                  TABLE I                                                         ______________________________________                                                          BROAD    PREFERRED                                          INGREDIENT        RANGE    RANGE                                              ______________________________________                                        Water (parts by weight)                                                                         100      100                                                Phenolic Sulfonate*                                                                             0.1-15     1-12                                             (active parts by weight)                                                      Cosurfactant (parts by weight)                                                                  0.05-15    1-7                                              Protective Agent (optional)                                                                     0.01-3   0.05-2                                             (parts by weight)                                                             NaCl (parts by weight)                                                                          0.1-10   0.1-8                                              ______________________________________                                         *The ranges for the active sulfonate in parts by weight. The "active"         value is readily determined by multiplying parts by weight used and the       percentage of active ingredients in the product.                         

The cosurfactant used in the surfactant system of this invention ispreferably one that is selected from the group consisting oforganonitriles and alcohols. The nitriles can be broadly characterizedas organonitriles having 1 to 3 --CN groups attached to carbon atoms incompounds containing a total of 2 to 40 carbon atoms and up to 4 oxygenand/or sulfur atoms and up to 4 additional nitrogen atoms. The preferrednitriles are acetonitrile, propionitrile, butyronitrile,α-methyleneglutaronitrile, tridecanenitrile, benzonitrile,phenylacetonitrile, acrylonitrile, methacrylonitrile, vinylacetonitrile,succinonitrile, 1,3-dicyanopropene, 1,3-dicyano-3-butene,tris(cyanoethyl)methane, 1,1-dicyanoethane and mixtures thereof. Thepreferred nitrile when used is acrylonitrile. The alcohols contemplatedas cosurfactants in accordance with this invention include alcoholshaving 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms. Examples ofuseful alcohols which can be employed as cosurfactants includeisopropanol, 1-butanol, isoamyl alcohol, isobutyl alcohol, hexanol,octanol, dodecanol, heptanol, decanol and mixtures thereof. Thepreferred alcohol cosurfactant is isoamyl alcohol.

Oil Recovery Process

A further embodiment of this invention resides in an oil recoveryprocess. This process involves generally the conventional steps of postprimary oil recovery and distinguishes over the known proceduresprimarily in the use of the novel compounds defined above and in thesurfactant system employing these novel compounds.

Preflush

It is optional, although not necessary, to carry out a preflush steppreceding the further oil recovery operation. Such preflush operationsare known in the art. Generally, a brine compatible with the surfactantsystem is injected via at least one injection well into the subterraneanformation. Such a brine typically contains 2000-50,000 ppm salts,predominantly sodium chloride. Preferably a brine solution as utilizedin the production of the surfactant system is also used in this preflushstep.

The quantity of the preflush employed will generally be in a range ofabout 0.01 to 2, preferably 0.25 to 1 pore volume, based on the totalpore volume of the formation or reservoir subjected to the recovery.

Surfactant Flooding

After the optional preflush step the surfactant system of this inventionis injected into the reservoir via at least one injection well. Thesurfactant system is injected in an amount usually in the range of about0.001 to 1.0, preferably 0.01 to 0.25 pore volume based again on thepore volume of the total treated and produced formation.

The preferred operation makes use of the surfactant system in a mannerthat a multiphase system including at least one microemulsion phase isformed in the formation. Usually the surfactant system contains as themain ingredients water, the surfactant including the sulfonated orsulfomethylated phenolic compound and the cosurfactant. Theseingredients are thoroughly mixed and then introduced into the formationvia one or more injection wells. However, the in-situ formation of amicroemulsion in the formation, e.g. by simultaneous but unmixedinjection or by alternating the injection of surfactant and cosurfactantis also within the scope of this invention.

Generally, the microemulsion is formed in the reservoir after thesurfactant system is injected as a solution containing surfactant andcosurfactant in brine.

The present invention can be utilized for a variety of subterraneanreservoirs. The invention is, however, particularly preferred inreservoirs containing hard brine connate water. Such hard brines arecharacterized by a high content of Mg++ and Ca++ ions in the reservoirwater. Typical hard brines contain more than 100 ppm of Ca++ and/orMg++. The concentration range of these ions extends to 10,000 ppm,usually to 1000 ppm.

If additional protective agents are employed in the surfactant system ofthis invention, they are utilized in the quantities shown above inaddition to the novel compositions of this invention. Examples for suchprotecting agents are polyethoxylated fatty alcohols and polyethoxylatedalkylphenols. In addition, the sodium salts of sulfated polyethoxylatedfatty alcohols and polyethoxylated alkylphenols are known in the art tofunction as protective agents.

Mobility Buffer

Following the surfactant slug it is presently preferred, although notnecessary, to inject a mobility buffer solution into the reservoir. Thisbuffer helps prevent fingering and enhances the efficiency of the oilrecovery. Buffer solutions are aqueous solutions of polymericviscosifiers or other thickening agents. Examples of useful mobilitybuffers are aqueous fluids containing mobility reducing agents such ashigh molecular weight partially hydrolyzed polyacrylamides,biopolysaccharides, soluble cellulose ethers and the like. The mobilitybuffer comprises 50 to 20,000, preferably 200 to 5,000 ppm of themobility reducing agent in the fluid.

The concentration of the thickening agent in the mobility buffer fluidcan remain constant over the injection period or the mobility bufferslug can be "graded", i.e., the viscosifier concentration starts out ata relatively high level at the beginning of the injection and theconcentration tapers off toward the end of the injection. As an example,the aqueous mobility buffer slug can start with a concentration of 2500ppm of polyacrylamide and be graded back by continuous dilution to 250ppm of polyacrylamide. The "grading" of mobility buffer fluids iswell-known in the art.

The following examples are intended to further illustrate the inventionwithout unduly limiting the scope thereof.

EXAMPLE I

This example describes the sulfomethylation of p-dodecylphenol.

A charge of 32.8 g (0.125 mol) of p-dodecylphenol, 63.0 g (0.50 mol) ofanhydrous sodium sulfite, 250 mL of water and 20 g (0.250 mol) of 37weight percent aqueous formaldehyde was placed in a 500 mLround-bottomed flask equipped with N₂ inlet tube, magnetic stirring barand water-cooled reflux condenser. The mixture was boiled at refluxunder a nitrogen atmosphere for a period of 20 hours. During thisperiod, the reaction mixture became a yellow pasty material suspended inwater but toward the end of the reflux period the reaction mass appearedto be a white crystalline suspension. The mixture was acidified to a pHof 6 with dilute aqueous sulfuric acid and the precipitate was collectedby filtration. This product was taken up in isopropanol and the solutionwas filtered to remove insoluble matter. The isopropanol filtrate wasstripped of volatiles on a rotary evaporator to leave 36.3 g of a whitecrystalline residue. Continuous extraction of this material withn-butanol yielded no additional product. An elemental analysis of theproduct gave the following results:

    ______________________________________                                                % C  66.9                                                                     % H  9.24                                                                     % S  5.06                                                             ______________________________________                                    

Theoretical percentage for sulfur is 8.47% in5-dodecyl-2-hydroxy-alphatoluenesulfonate. The above product is about60% pure based on percent sulfur found in the above analysis.Presumably, the major component in the white crystalline residue issodium 5-dodecyl-2-hydroxy-alphatoluenesulfonate.

EXAMPLE II

This example describes the sulfomethylation of p-nonylphenol.

A charge of 110 g (0.5 mol) p-nonylphenol and 500 mL of an aqueousmixture containing 126 g (1.0 mol) anhydrous sodium sulfite and 26.5 g(0.25 mol) anhydrous sodium carbonate was placed in a 1-literround-bottomed flask equipped with magnetic stirring bar and watercooledreflux condenser. This mixture was stirred vigorously as 60.5 g (22.5 g,0.75 mol CH₂ O) of 37 weight percent aqueous formaldehyde was added in adropwise fashion over a 30 minute period. The stirred mixture was thenboiled at reflux for about 14 hours. The milky gelatinous mixture wascooled to room temperature, acidified to a pH of 6 with aqueous sulfuricacid and extracted with chloroform. The chloroform phase was separatedand stripped on a rotary evaporator to give a white crystalline solidwhich weighed 118.7 g. By hyamine titration (sulfonate determination) avalue of 2.03 meq/g was determined. Theory for sodium5-nonyl-2-hydroxy-alpha-toluenesulfonate (Formula Weight 336) is 2.98meq/g. Based on these equivalent weight values the reaction product wasabout 68% pure.

The following experimental procedure was used to condition sandstonecores for surfactant flood runs to demonstrate the effectiveness of theinventive material in tertiary oil recovery.

Experimental General

Berea sandstone cores of the desired length and 3 inches in diameterwere dried under vacuum for 24 hours at 250° F. Polycarbonate disc endplates with centrally located 1/8" threaded openings were secured toeach end of the core with epoxy adhesive before applying an epoxycoating to the outside surface of the core. The epoxy coating materialwas formulated by mixing 550 g of a commercially available epoxy resin,50 g of a suitable activator and 140 g diatomaceous earth. This mixturewas stirred until smooth before applying to the surface of the core. Thecores were rotated continuously as the epoxy mixture was applied with a2" paint brush. Four gauze strips measuring 2"×12" were applied to thecore in the following manner: a first gauze strip was applied to thecore and covered with epoxy as the core was rotated; the remaining threestrips were then individually incorporated in a similar manner. The corecoating was cured over a period of about 4 hours at ambient temperatureas the core was rotated. One-eighth inch male connector fittings wereplaced on each end of the core and pipe plug caps were put on the core.

The core was weighed to determine the dry weight before being saturatedwith brine of the desired concentration. A vacuum of about 1 mm waspulled on the core before saturating the core with approximately 500 mLof brine. After saturation, approximately 100 to 200 mL of brine werepumped through the core before determining the original permeability towater. A 1 mL portion of effluent brine was collected from the saturatedcore and thereafter during a period of one minute, the volume ofadditional effluent collected and the pressure in psi were recorded.With these values the original permeability to water, e.g., on the orderof 3.2 mL/min at 43 psi could be recorded. The pore volume of the corewas calculated by the relationship: ##EQU1##

The brine-saturated core was oil flooded in the conventional manneruntil oil break-through became detectable by the presence of alternateglobules of oil and water in the effluent line. The oil flood wascarried out to completion by the 24 hour recycling of oil through thecore to remove all of the displaceable water. The total water displaced,i.e., water displaced at the point of oil break-through and waterdisplaced by the 24 hour recycle procedure was recorded as waterdisplaced by oil flood. If desired, oil permeability was determined in amanner analogous to that used above for establishing originalpermeability to water. Prior to waterflood, the effluent line was airblown to remove oil.

The oil-flooded core was waterflooded in the conventional manner untilwater break-through became detectable by the presence of alternateglobules of oil and water in the effluent line. The waterflood wascarried to completion by the 24 hour recycling of water through the coreto remove all of the displaceable oil. The total oil displaced, i.e.,oil displaced at the point of water break-through and oil displaced bythe 24 hour recycle procedure was recorded as oil displaced bywaterflood. If desired, water permeability after waterflood can bedetermined in a manner analogous to that used above for originalpermeability to water. The residual oil volume remaining in the core wascalculated by subtracting the oil volume displaced by the waterfloodfrom the water volume displaced by the oilflood. At this point, the coresimulated an oil reservoir which had been exhaustively waterflooded.Cores were routinely conditioned in this manner prior to carrying outsurfactant flood tests.

The following example shows the effectiveness of the sulfomethylatednonylphenol composition as a surfactant in recovering oil from waterwetBerea sandstone cores.

EXAMPLE III

Surfactant flooding of a waterwet Berea sandstone core was carried outin the conventional manner, i.e., sequential injection of surfactantslug, mobility buffer and drive water. The preparation of the surfactantis described in Example II. The core run result is shown in Table II.

                  TABLE II                                                        ______________________________________                                        Run  % PV Surfactant                                                                            Added Co- % Tertiary                                                                            Salinity                                  No.  Slug         surfactant                                                                              Recovery                                                                              Wt. % NaCl                                ______________________________________                                        1    25           IAA*      81.8    3.0                                       ______________________________________                                         *IAA represents isoamyl alcohol (3.0 wt. % of the surfactant slug).      

Referring to Table II, it is evident that the sulfomethylated derivativeof p-nonylphenol is an effective surfactant for recovering waterfloodresidual oil from a waterwet Berea sandstone core at a salinity of 3.0weight percent NaCl.

EXAMPLE IV

This example describes the sulfonation of p-dodecylphenol and the use ofthe reaction product as a surfactant in recovery of waterflood residualoil from Berea sandstone cores.

A charge of 100 g (0.381 mol) p-dodecylphenol was placed in a 400 mLbeaker equipped with a magnetic stirring bar and placed on a stirrerhot-plate. The phenol was stirred at ambient temperature during the slowaddition of 30 mL fuming sulfuric acid. After the heat of reaction hadsubsided, the stirred reaction mass was warmed briefly before beingcooled to ambient temperature and stirred an additional 14 hours. Thereaction mixture was neutralized with aqueous sodium hydroxide,transferred to a separatory funnel and extracted successively with 100mL portions of hexane. The hexane extracts were combined andconcentrated on a rotary evaporator to a viscous reddish-brown coloredliquid. The water phase was concentrated and dried to a solid residue ina rotary evaporator. This residue was further dried by the addition oftoluene and stripping. This solid was partially soluble in acetone: theacetone-insoluble portion was filtered off and treated with ethanol. Theethanol-insoluble matter was separated by filtration and the ethanolsoluble material was isolated by stripping the ethanol to give aresidual light yellow powder which weighed about 24.5 g. An infraredspectrum analysis of this material verified the presence of sulfonategroups. The active sulfonate surfactant species in this material waspresumably sodium dodecylphenol sulfonate.

EXAMPLE V

Surfactant flooding of a waterwet Berea core containing waterfloodresidual oil was carried out in the conventional manner, i.e.,sequential injection of preflush slug, surfactant slug and mobilitybuffer. The preflush slug was a 50% PV solution containing 2.0 weightpercent sodium chloride and 2.07 weight percent isoamyl alcohol. Thesurfactant slug was a 10% PV solution containing 3.12 weight percent ofthe light yellow powder reaction product (sodium p-dodecylphenolsulfonate) made in Example IV, 2.07 weight percent isoamyl alcohol, 2.0weight percent sodium chloride and 1750 ppm soluble calcium ion. Themobility buffer slug was a 43 centipoise solution of Betz Hi-Vispolyacrylamide in Arkansas-Burbank river water (<500 ppm total dissolvedsolids) graded back logarithmically with Arkansas-Burbank water. Thecore run result is summarized in Table III.

                  TABLE III                                                       ______________________________________                                        Run  % PV Surfactant                                                                            Added Co- % Tertiary                                                                            Salinity                                  No.  Slug         surfactant                                                                              Recovery                                                                              Wt. % NaCl                                ______________________________________                                        2    10           IAA*      61      2.0                                       ______________________________________                                         *IAA represents isoamyl alcohol.                                         

Referring to Table III, it is evident that the sulfonated derivative ofp-dodecylphenol is an effective surfactant for recovering waterfloodresidual oil from a Berea sandstone core.

EXAMPLE VI

This example demonstrates that an inventive anionic surfactant such asthe sulfomethylated derivative of dodecylphenol is partitioned mostlyinto the aqueous phase of a heptane/isobutyl alcohol/hard brine systemwherein the brine contains a significant concentration of Ca⁺⁺. Controlruns contained a commercially available sodium petroleum sulfonate(Witco Chem. Co. TRS10-410) and it was observed that the petroleumsulfonate surfactant was partitioned almost entirely into the heptanephase of said heptane/isobutyl alcohol/hard brine system.

A mixture was prepared by combining 180 mL of distilled water, 1.9 ganhydrous Na₂ CO₃, 6.9 mL isobutyl alcohol and 5.4 g (8:59 mmols, 60.1%active basis) of sulfomethylated dodecylphenol. To this mixture wasadded 4.3 mL of 1M CaCl₂ solution (4.3 mmols Ca⁺⁺). This solution wasequilibrated with heptane (50 mL) by stirring for about 2 hours atambient temperature and then allowed to stand for about 48 hours topermit the organic and aqueous phases to separate.

Analysis showed that 76.1% of the inventive sulfomethylateddodecylphenol was present in the aqueous phase and the remainingsulfonate (23.9%) was solubilized into the heptane phase.

For the control runs, the procedure was as follows:

C-5

A charge of 100 g (0.0861 mol/l.) of petroleum sulfonate, active basis)of deoiled TRS10-410 solution and 25.2 g of 0.340M CaCl₂ solution (8.61mmols of Ca⁺⁺) was placed in a 250 mL Erlenmeyer flask. A whiteprecipitate formed immediately on mixing and the mixture was stirredovernight at ambient temperature. A 20 mL portion of heptane and a 3 mLportion of isobutyl alcohol was added to the mixture and stirring wascontinued for two days.

The stirring was stopped and after standing at ambient temperature for 6hours, two transparent phases formed and a very small amount of whitesolid was evident at the interface. A sample of the aqueous phase onanalysis showed the presence of 0.0014 meq of sulfonate/g of aqueousphase. Since the original deoiled solution of TRS10-410 contained 0.086meq of petroleum sulfonate, it is evident that about 1.6% of thesulfonate was present in the aqueous phase and the remaining 98.4% ofthe sulfonate was solubilized into the heptane phase presumably as therelatively oil-soluble calcium salt form.

C-1

The procedure was essentially the same as C-5 except 12.6 g (4.3 mmolsCa⁺⁺) of a 0.340M CaCl₂ solution was used.

A sample of the aqueous phase on analysis showed the presence of 0.0016meq of sulfonate/g of aqueous phase. Thus, it is evident that about 1.8%of the sulfonate was present in the aqueous phase and the remaining98.2% of the petroleum sulfonate was solubilized into the heptane phasepresumably as the relatively oil-soluble calcium salt form.

C-2

This procedure was essentially identical to C-5 except the stocksolution of deoiled TRS10-410 petroleum sulfonate was prepared in 1weight percent aqueous sodium chloride solution rather than distilledwater.

Analysis showed 1.4% of the sulfonate in the aqueous phase and theremaining 98.6% of the petroleum sulfonate was solubilized into theheptane phase presumably as the relatively oil-soluble calcium saltform.

C-3

This procedure was similar to that used in C-5 except that no divalentcations such as Ca⁺⁺ or Mg⁺⁺ were present.

A sample of the aqueous phase (after the equilibrium of the TRS10-410stock solution with 20 mL of heptane and 3 mL isobutyl alcohol) onanalysis showed the presence of 0.078 meq of sulfonate/g of aqueousphase. Thus, it is evident that approximately 90.6% of the sulfonate waspresent in the aqueous phase and 9.4% of the relatively oil-insolublesodium salt form of the petroleum sulfonate was in the heptane phase.

C-4

This procedure was essentially the same as C-5 except 6.3 g (2.15 mmolsCa⁺⁺) of a 0.340M CaCl₂ solution was used.

A sample of the aqueous phase on analysis showed the presence of 0.0027meq of sulfonate/g of aqueous phase. Thus, it is evident that about 3.1%of the sulfonate was present in the aqueous phase and the remaining96.9% of the petroleum sulfonate was solubilized into the heptane phasepresumably as the relatively oil-soluble calcium salt form.

C-6

This procedure was essentially the same as C-5 above except 35 g of a0.246M MgCl₂ solution (8.61 mmols Mg⁺⁺) was used.

A sample of the aqueous phase on analysis showed the presence of 0.0012meq of sulfonate/g of aqueous phase. Thus, it is evident that about 1.4%of the sulfonate was present in the aqueous phase and the remaining98.6% of the petroleum sulfonate was solubilized into the heptane phasepresumably as the relatively oil-soluble magnesium salt form.

C-7

This procedure was essentially the same as C-6 above except 17.5 g of a0.246M MgCl₂ solution (4.3 mmols Mg⁺⁺) was used.

A sample of the aqueous phase on analysis showed the presence of 0.0019meq of sulfonate/g of aqueous phase. Thus, it is evident that about 2.2%of the sulfonate was present in the aqueous phase and the remaining97.8% of the petroleum sulfonate was solubilized into the heptane phasepresumably as the relatively oil-soluble magnesium salt form.

Results are summarized in Table IV.

                  TABLE IV                                                        ______________________________________                                        Partitioning of Surface Active Sulfonates in                                  Heptane/Isobutyl Alcohol/Hard Brine Systems                                                         % Sulfonate                                             Run Type  Sulfonate mmols   mmols H.sub.2 O                                                                           Heptane                               (C = Control)                                                                           Used      Ca.sup.++                                                                             Mg.sup.++                                                                           Phase Phase                                 ______________________________________                                        Invention SMDP.sup.#                                                                              4.3     None  76.1  23.9                                  C-1       TRS10-410.sup.a                                                                         4.3     None  1.8   98.2                                  .sup. C-2.sup.b                                                                         TRS10-410.sup.                                                                          4.3     None  1.4   98.6                                  .sup. C-3.sup.c                                                                         TRS10-410.sup.                                                                          None    None  90.6  9.4                                   C-4       TRS10-410.sup.a                                                                          2.15   None  3.1   96.9                                  C-5       TRS10-410.sup.a                                                                         8.6     None  1.6   98.4                                  C-6       TRS10-410.sup.a                                                                         None    8.6   1.4   98.6                                  C-7       TRS10-410.sup.a                                                                         None    4.3   2.2   97.8                                  ______________________________________                                         .sup.# SMDP represents the inventive sulfomethylated dodecylphenol.           .sup.a A stock solution of deoiled TRS10410 (Witco Chem. Co. petroleum        sulfonate, sodium salt form; average equivalent weight 418) was prepared      by combining 18 g of the deoiled sulfonate with 482 g distilled water.        This solution contained approximately 8.6 mmols of sulfonate per 100 g        portions used in each of the above equilibrations.                            .sup.b The stock solution of deoiled TRS10410 contained 1 wt. % NaCl.         .sup.c An 87.5 g portion rather than a 100 g portion of the deoiled           TRS10410 stock solution was used in this run.                            

Referring to the control run C-3, it is evident that equilibration ofpetroleum sulfonate (sodium salt form) in the system H₂O/heptane/isobutyl alcohol results in the majority of the petroleumsulfonate partitioning into the aqueous phase. Referring to theremaining control runs (C-1, C-2 and C-4 through C-7), it is evidentthat the addition of divalent cations such as Ca⁺⁺ or Mg⁺⁺ to theequilibration system results in the partitioning of the petroleumsulfonate into the heptane phase presumably as the relativelyoil-soluble divalent cation salts form. In sharp contrast, thepartitioning of the inventive sulfomethylated dodecylphenol (seeInvention Run) in a Ca⁺⁺ containing system was distributed between intothe aqueous phase and the heptane phase. Similar control runs (see C-1and C-2) with comparable Ca⁺⁺ concentrations, showed partitioning ofpetroleum sulfonate mostly to the heptane phase rather than the aqueousphase.

Reasonable variations and modifications which will become apparent tothose skilled in the art can be made from this invention withoutdeparting from the spirit and scope thereof.

That which is claimed is:
 1. Surfactant composition comprisingbrine, asulfonated composition produced by a process comprising reacting aphenolic material comprising one or more alkyl substituted hydroxyaromatic compounds having the formula ##STR7## wherein R is alkyl having1 to 30 carbon atoms, with the proviso that at least one radical R has 6to 30 carbon atoms, wherein n is a number from 1 to 3, Ar is asubstituted or unsubstituted aromatic hydrocarbyl moiety having the --OHand the X in ortho position to each other, connected to neighboringaromatic carbons, wherein X is hydrogen, with the proviso that the totalnumber of carbons in all n radicals R and the aromatic moiety Artogether are in the range of 12 to about 40, with a sulfonating agent toproduce a sulfonic acid intermediate having an --SO₃ H group in orthoposition to the --OH group of the starting material, and neutralizingthis sulfonic acid intermediate product with a base to produce asulfonate having the formula ##STR8## wherein R, n, Ar have the meaningas defined above and wherein Cat is selected from the group consistingof --Na, --K and --NHR₃.sup.(1) wherein R.sup.(1) is hydrogen or analkyl radical having 1 to 3 carbon atoms or hydroxyalkyl with 2 or 3carbon atoms, and a cosurfactant.
 2. Surfactant compositioncomprisingbrine, a sulfonated alkyl phenol composition having theformula ##STR9## wherein R is alkyl or alkenyl having 1 to 30 carbonatoms, with the proviso that at least one radical R has 6 to 30 carbonatoms, wherein n is a number from 1 to 3, Ar is a substituted orunsubstituted aromatic hydrocarbyl moiety having the --OH and the Z inortho position to each other, connected to neighboring aromatic carbons,wherein Z is a radical selected from the group consisting of --SO₃ --Cator --CH₂ --SO₃ --Cat wherein Cat is selected from the group consistingof --Na, --K and --NHR₃.sup.(1) with the further proviso that the totalnumber of carbon atoms per molecule is 12 to about 40, and acosurfactant.
 3. Surfactant composition in accordance with claim 2wherein said sulfonated composition is an alkyl substituted phenolcompound having the radical Z attached to an aromatic carbon atom inortho position with respect to a OH substituted aromatic carbon atom. 4.Surfactant composition as defined in claim 3 wherein Cat is Na. 5.Surfactant composition as defined in claim 3 wherein the total number ofhydroxyl groups attached to aromatic carbon atoms is 1 to 3 and whereinthe total --SO₃ Cat groups present in the molecule is 1 to
 3. 6.Surfactant composition as defined in claim 25 characterized in that itcomprises a plurality of chemical compounds defined by this formula. 7.Surfactant composition as defined in claim 3 wherein said sulfonatedcomposition is a sulfonated or sulfomethylated alkyl phenol. 8.Surfactant composition as defined in claim 3 wherein said sulfonatedcomposition is an alkyl substituted sulfonated or sulfomethylatedbis-phenol.
 9. Surfactant composition as defined in claim 3 wherein saidsulfonated composition is an alkyl substituted naphthol.
 10. Surfactantcomposition in accordance with one of the claims 1 to 9 wherein saidcosurfactant is selected from the group consisting of alcohols having 3to 8 carbon atoms and organonitrile compounds having 2 to 40 carbonatoms.
 11. Surfactant composition in accordance with claim 1 wherein thephenolic starting material is selected from the group consisting ofalkyl substituted phenols, alkyl substituted bis-phenols and alkylsubstituted naphthols.
 12. Surfactant composition in accordance withclaim 1 wherein Cat is sodium.
 13. Surfactant composition in accordancewith claim 1 wherein said sulfonating agent is selected from the groupconsisting of concentrated sulfuric acid, SO₃ and solutions of SO₃ inSO₂ or fuming sulfuric acid.
 14. Surfactant composition in accordancewith claim 1 wherein said phenolic starting material is a mixture of aplurality of phenolic compounds.
 15. Surfactant composition inaccordance with claim 1 wherein said mixture of phenolic compounds isderived from by-product hydrocarbon process streams.
 16. Surfactantcomposition comprisingbrine, a sulfonated composition produced by aprocess comprising reacting a phenolic material comprising one or morealkyl substituted hydroxy aromatic compounds having the formula##STR10## wherein R is alkyl or alkenyl having 1 to 30 carbon atoms,with the proviso that at least one radical R has 6 to 30 carbon atoms,wherein n is a number from 1 to 3, Ar is a substituted or unsubstitutedaromatic hydrocarbyl moiety having the --OH and the X in ortho positionto each other, connected to neighboring aromatic carbons, X is hydrogen,with the proviso that the total number of carbons in all n radicals Rand the aromatic moiety Ar together are in the range of 12 to about 40,with formaldehyde in the presence of a sulfonating agent to produce acompound having the formula ##STR11## wherein R, n, Ar have the meaningas defined above and wherein Cat is selected from the group consistingof --Na, --K and --NHR₃.sup.(1) wherein R.sup.(1) is hydrogen or analkyl radical having 1 to 3 carbon atoms or hydroxyalkyl with 2 or 3carbon atoms, and a cosurfactant.
 17. Surfactant composition inaccordance with claim 16 wherein the phenolic starting material isselected from the group consisting of alkyl substituted phenols, alkylsubstituted bis-phenols and alkyl substituted naphthols.
 18. Surfactantcomposition in accordance with claim 16 wherein Cat is sodium. 19.Surfactant composition in accordance with claim 16 wherein saidsulfonating agent is selected from the group consisting of sulfite saltscharacterized by the formula

    (Cat).sub.1 or 2 (H).sub.1 or 0 SO.sub.3

wherein Cat has the same meaning as defined in claim
 16. 20. Process forhydrocarbon recovery from subterranean formation comprising(a) injectinga surfactant comprising a sulfonated alkyl phenol compound having theformula ##STR12## into said formation via at least one injection well,wherein R is alkyl or alkenyl having 1 to 30 carbon atoms, with thepriviso that at least one radical R has 6 to 30 carbon atoms, wherein nis a number from 1 to 3, Ar is a substituted or unsubstituted aromatichydrocarbyl moiety having the --OH and the Z in ortho position to eachother, connected to neighboring aromatic carbons, wherein Z is a radicalselected from the group consisting of --SO₃ --Cat or --CH₂ --SO₃ --Catwherein Cat is selected from the group consisting of --Na, --K and--NHR₃.sup.(1) with the further proviso that the total number of carbonatoms per molecule is 12 to about 40 (b) causing the so injectedsurfactant to move from the injection well towards one or moreproduction wells displacing hydrocarbon present in said formation, (c)recovering displaced hydrocarbon from at least one of said productionwells.
 21. Process for hydrocarbon recovery from subterranean formationcomprising(a) injecting a surfactant comprising an alkyl substitutedsulfonate phenolic compound produced by a process comprising reacting aphenolic material comprising one or more alkyl substituted hydroxyaromatic compounds having the formula ##STR13## wherein R is alkylhaving 1 to 30 carbon atoms, with the proviso that at least one radicalR has 6 to 30 carbon atoms, wherein n is a number from 1 to 3, Ar is asubstituted or unsubstituted aromatic hydrocarbyl moiety having the --OHand the X in ortho position to each other, connected to neighboringaromatic carbons, wherein X is hydrogen, with the proviso that the totalnumber of carbons in all n radicals R and the aromatic moiety Artogether are in the range of 12 to about 40, with a sulfonating agent toproduce a sulfonic acid intermediate having an --SO₃ H group in orthopositions to the --OH group of the starting material, and neutralizingthis sulfonic acid intermediate product with a base to produce asulfonate having the formula ##STR14## wherein R, n, Ar have the meaningas defined above and wherein Cat is selected from the group consistingof --Na, --K and --NHR₃.sup.(1) wherein R.sup.(1) is hydrogen or a alkylradical having 1 to 3 carbon atoms or hydroxyalkyl with 2 or 3 carbonatoms, into said formation via at least one injection well, (b) causingthe so injected surfactant to move from the injection well towards oneor more production wells displacing hydrocarbon present in saidformation, (c) recovering displaced hydrocarbon from at least one ofsaid production wells.
 22. Process for hydrocarbon recovery fromsubterranean formation comprising(a) injecting a surfactant comprisingan alkyl substituted, sulfomethylated phenolic compound produced by aprocess comprising reacting a phenolic material comprising one or morealkyl substituted hydroxy aromatic compounds having the formula##STR15## wherein R is alkyl or alkenyl having 1 to 30 carbon atoms,with the proviso that at least one radical R has 6 to 30 carbon atoms,wherein n is a number from 1 to 3, Ar is a substituted or unsubstitutedaromatic hydrocarbyl moiety having the --OH and the X in ortho positionto each other, connected to neighboring aromatic carbons, X is hydrogen,with the proviso that the total number of carbons in all n radicals Rand the aromatic moiety Ar together are in the range of 12 to about 40,with formaldehyde in the presence of a sulfonating agent to produce acompound having the formula ##STR16## wherein R, n, Ar have the meaningas defined above and wherein Cat is selected from the group consistingof --Na, --K and --NHR₃.sup.(1) wherein R.sup.(1) is hydrogen or analkyl radical having 1 to 3 carbon atoms or hydroxyalkyl with 2 or 3carbon atoms via at least one injection well, (b) causing the soinjected surfactant system to move from the injection well towards oneor more production wells displacing hydrocarbon present in saidformation, (c) recovering displaced hydrocarbon from at least one ofsaid production wells.
 23. Process in accordance with claim 20 wherein amobility buffer fluid is injected into said subterranean formationfollowing said surfactant.
 24. Process in accordance with claim 21wherein a mobility buffer fluid is injected into said subterraneanformation following said surfactant.
 25. Process in accordance withclaim 22 wherein a mobility buffer fluid is injected into saidsubterranean formation following said surfactant.
 26. Process inaccordance with claim 23 wherein an aqueous drive fluid in injected intosaid subterranean formation following said mobility buffer fluid. 27.Process in accordance with claim 24 wherein an aqueous drive fluid ininjected into said subterranean formation following said mobility bufferfluid.
 28. Process in accordance with claim 25 wherein an aqueous drivefluid in injected into said subterranean formation following saidmobility buffer fluid.
 29. Process in accordance with claim 20 whereinsaid surfactant further comprises a protective agent.
 30. Process inaccordance with claim 21 wherein said surfactant further comprises aprotective agent.
 31. Process in accordance with claim 22 wherein saidsurfactant further comprises a protective agent.
 32. Process inaccordance with claim 20 wherein said surfactant is injected into aformation containing hard brine.
 33. Process in accordance with claim 21wherein said surfactant is injected into a formation containing hardbrine.
 34. Process in accordance with claim 22 wherein said surfactantis injected into a formation containing hard brine.
 35. Process inaccordance with claim 22 wherein the phenolic starting material isselected from the group consisting of alkyl substituted phenols, alkylsubstituted bis-phenols and alkyl substituted naphthols.
 36. Process inaccordance with claim 22 wherein Cat is sodium.
 37. Process inaccordance with claim 22 wherein said sulfonating agent is selected fromthe group consisting of sulfite salts characterized by the formula

    (Cat).sub.1 or 2 (H).sub.1 or 0 SO.sub.3

wherein Cat has the same meaning as defined in claim
 22. 38. Process inaccordance with claim 24 wherein the phenolic starting material isselected from the group consisting of alkyl substituted phenols, alkylsubstituted bis-phenols and alkyl substituted naphthols.
 39. Process inaccordance with claim 21 wherein Cat is sodium.
 40. Process inaccordance with claim 24 wherein said sulfonating agent is selected fromthe group consisting of concentrated sulfuric acid, SO₃ and solutions ofSO₃ in SO₂ or fuming sulfuric acid.
 41. Process in accordance with claim21 wherein said phenolic starting material is a mixture of a pluralityof phenolic compounds.
 42. Process in accordance with claim 21 whereinsaid mixture of phenolic compounds is derived from by-producthydrocarbon process streams.